Organically substituted sodium aluminum hydrides and method of making and using the same

ABSTRACT

1. A SUBSTITUTED SODIUM ALUMINUM HYDRIDE OF THE FORMULA NAA1HXQ-4, WHEREIN X IS 1 OR 2 AND WHEREIN Q IS AN ORGANIC RESIDUE DERIVED BY SPLITTING OFF AN ACTIVE HYDROGEN ATOM FROM A COMPOUND SELECTED FROM THE GROUND CONSISTING OF: (1) ETHER ALCOHOLS OF THE FORMULA R&#39;&#39;O(CH2)ZOH WHERE R&#39;&#39; IS ALKYL OF 1 TO 4 CARBON ATOMS AND Z IS AN INTEGER FROM 2 TO 4; (2) POLYETHER ALCOHOLS OF THE FORMULA   R&#39;&#39;(OCH2)NOC(CH2)ZOH   WHEREIN N IS AN INTEGER FROM 2 TO 4 AND R&#39;&#39; AND Z HAVE THE SAME MEANING AS IN (1) ABOVE; (3) AN AMINO ALCOHOL OF THE GENERAL FORMULA   R&#34;R&#34;&#39;&#39;N(CH2)ZOH   WHEREIN R&#34; AND R&#34;&#39;&#39; ARE EACH SELECTED FROM THE GROUP CONSISTOING OF RO(CH2)Z AND R, AND WHEREIN R IS SELECTED FROM THE GROUP CONSISTING OF ALKYL OF 1 TO 4 CARBON ATOMS AND ARYL OF 6 TO 8 CARBON ATOMS, AND WHEREIN Z HAS SAME MEANING AS IN (1) ABOVE.

United States Patent ORGANICALLY SUBSTITUTED SODIUM ALUMI- NUM HYDRIDES AND METHOD OF MAKING AND USING THE SAME Jaroslav Vit, Bohuslav Casensky, and Milan Mamula,

Prague, and Jiri Machacek, Rez, Czechoslovakia, assignors to Ceskoslovenska Akademie Ved, Prague, Czechoslovakia No Drawing. Filed Nov. 10, 1966, Ser. No. 594,971 Claims priority, application Czechoslovakia, Nov. 13, 1965, 6,771/65; Mar. 26, 1966, 2,009/66, 2,010/66 Int. Cl. C011) 6/28; (307i /06 US. Cl. 260-448 AD 10 Claims The present invention relates to a method of producing substituted aluminum hydrides, to novel substituted aluminum hydrides and to a method of carrying out reductions and a method of utilizing substituted aluminum hydrides as reducing agents and as catalysts.

More particularly, the present invention is concerned with a method of producing sodium aluminum hydrides which are substituted with organic groups, with novel sodium aluminum hydrides substituted with organic groups, and with a method of carrying out reductions and catalytically favored direct synthesis, utilizing the novel organically substituted aluminum hydrides of the present invention.

Certain organically substituted sodium aluminum hydrides, for instance sodium aluminum ethoxy hydride, methoxy hydride and aryloxy hydrides are known and used as specific reducing agents in organic chemistry. It is possible, for instance, by using these compounds as reducing agents to reduce aldehydes, ketones and organic acid esters and chlorides to alcohols, to reduce nitro-compounds to amines and nitriles to aldehydes. Furthermore, these compounds are useful as dehalogenating agents.

Various processes have been described for producing these compounds.

One of the difiiculties encountered in producing these compounds and also in using the same is that they are only soluble in very few organic solvents, for instance in diethyl ether but not in solvents which are more easily available and less dangerous to handle. Thus, for instance, it is not possible to dissolve the above mentioned organically substituted sodium aluminum hydrides in benzene.

This limited solubility creates difficulties and dangers in the production as well as in the use of these known products.

Some other hydrides for instance decaborane are soluble in non-polar media, however, in such solution these hydrides do not possess any reducing properties.

It is therefore an object of the present invention to overcome the above mentioned dilficulties and disadvantages.

It is a further object of the present invention to provide a method for producing organically substituted sodium aluminum hydrides which can be carried out in a simple and economical manner. It is yet another object of the present invention to provide a method for producing organically substituted sodium aluminum hydrides which can be carried out in a non-polar media.

It is still a further object of the present invention to provide organically substituted sodium aluminum hydrides which are soluble in certain organic non-polar media such as benzene, toluene and the like.

It is still another object of the present invention to provide a method of carrying out reducing reactions, utilizing organically substituted sodium aluminum hydrides as the reducing agents, which reactions can be carried out in a non-polar media.

3,652,622 Patented Mar. 28, 1972 "ice wherein x is an integral number between 1 and 2 inclusive and Z is selected from the group consisting of Q and Y, wherein Y is selected from the group consisting of methoxyl, ethoxyl and propoxyl, and wherein Q is an organic radical, derived by splitting off an active hydrogen atom from a compound selected from the group consisting of:

(1) Tetrahydrofurfuryl alcohols,

(2) Tetrahydropyranyl alcohols,

(3) Ether alcohols of the type obtainable by alkylat- I ing one hydroxyl group in diols or two hydroxyl groups in triols.

(4) Polyether alcohols of the type obtainable by dehydration of ether alcohols and diols or by dehydration of tetrahydrofurfuryl alcohols and diols, or by dehydration of tetrahydropyranyl alcohols and diols,

(5) The compounds of groups (1)-(4), wherein at least one oxygen atom is replaced by a sulphur atom,

(6) An amino alcohol of the general formula wherein R" and R are each selected from the group consisting of alkoxyalkyl of the formula RO(CH and R, and wherein R is selected from the group consisting of alkyl with 1-4 carbon atoms and aryl with 6-8 carbon atoms, and wherein z is an integral number between 2 and 4 inclusive, comprising the step of reacting at least one substance selected from the group consisting of Na AlH and NaAlH, with a compound of the general formula A12 wherein Z has the same meaning as defined above.

The term propoxyl is meant to denote not only normal propoxyl but also isopropoxyl.

Na AlH may be prepared for instance by the method described in Czechoslovak Pat. No. 117,768.

Compounds of the general formula A12 and also of the general formula NaZ which may be also used as a supplementary reactant as will be described in detail further below, may be prepared by the reaction of the respective alcohol with the metal, i.e., with sodium or aluminum, or with the respective hydride, i.e., sodium hydride or aluminum hydride. There is no difiiculty involved in preparing the thioalkoxy, dialkylamino and alkylamino substituted derivatives. In the case of the preparation of the thioalcoholates of the type NaZ and AlZ however, it is recommended to start from the more reactive hydrides NaH and AlH instead of the metals. The reactions, generally, may be carried out in liquid media such as hydrocarbons, ethers (diethylether, monoglyme, tetrahydrofurane) using an excess on the ZH compounds.

The thus formed NaZ compounds are insoluble in the reaction medium and thus will be formed as a suspension.

Prior to being used in the above described process of the present invention which may be carried out for instance as described in Equations 7-l3 and 15-19 below, the NaZ compounds must be separated from the suspension preferably by filtration and subsequent drying. The

thus obtained dry product may be used directly as a starting material for the method of the present invention. It does not require any further purification. The impurities which might be present such as metallic sodium do not interfere with the reaction since these impurities are insoluble in the reaction medium, whereas the finished products obtained by the method of the present invention will be soluble in the respective reaction medium. However, if the compound of the type NaZ has been made by using NaH as starting material and therefore the thus produced NaZ may contain residual NaH it might be desirable in certain cases to increase in the method according to the present invention the amount of the sodium aluminum hydride and of A12 above the theoretically required amount.

The preparation of alcoholates, aminoalcoholates, and thioalcoholates of the type AlQ is equally simple. Conventional methods may be used in the preparation of all derivatives, starting from the aluminum or aluminum hydride, and the respective alcohol, aminoalcohol or thioalcohol of the formula QH, the later being easily removed from the product AlQ when stripping off the solvent; subsequently, the product AlQ is dried in vacuo. The above sodium aluminum hydrides, substituted according to this invention are all soluble in hydrocarbons and ethers; thus unaltered aluminum or aluminum hydride can be easily removed by filtration prior to the actual isolation of the final product. The thioalkoxy-derivatives, however, having a SAl bond in their molecule, are distinguished by somewhat lower solubility.

Another very advantageous method of producing aluminum alcoholates and thioalcoholates of the type AlQ is based on the following equilibrium reaction:

It is advisable to use an excess of QH and to carry out the reaction under simultaneous removal of CH OH (01 ROH), the boiling point of which must be lower than that of QH, which usually will be the case. The stripping off of the CH OH (ROH) may be conveniently carried out by using a rectification column.

The starting aluminum alcoholates to carry out the reaction are easily accessible in a Pure state, even on an industrial scale. To start from Al(OCH seems to be most advantageous since the same is insoluble, e.g., in hydrocarbons, thus facilitating the separation of any unaltered portion thereof from the reaction mixture. The product AlQ may be isolated by simply stripping off the solvent and the excess of QH.

The starting compound of the type NaZ.AlZ may be prepared by the reactions accounted for as below:

The complex alcoholates of the type NaZ.AlZ are generally easily soluble in ethers and the NaQAlQ alcoholates even in aromatic hydrocarbons. Thus, they may be easily prepared according to the equations given above under the same conditions as when starting from simple alcoholates of the type NaZ+AlZ The method of the present invention may be carried out in accordance with the following equations:

In a similar manner complex compounds of the general formula NaZ.A1Z may be used instead of A12 for in- 4 stance in accordance with the equations 15-17 further below.

It is general known that sodium alcoholates and aluminum alcoholates react to yield complex alcoholates according to the following equation:

wherein X is an alkyl or an aryl. The only condition for carrying out this reaction is that of solubility. Al(OX) and the product NaAl(OX) must be soluble in the solvents used. The alcoholates of the type AlQ and NaQ.AlQ are generally more easily soluble in ethers and in aromatic hydrocarbons than the alcoholates of the type Na(OX).Al(OX) wherein X is the same as mentioned above and they always result as an intermedial product of the reactions 7 to 13. If the complex alcoholates of the type NaZ.AlZ are used as the starting product according to our invention the respective reactions are accounted for by the following equations:

The liquid reaction medium on which the above described reactions of the present invention are carried out is preferably selected from the group consisting of hydrocarbons and ethers which at atmospheric pressure have a boiling point lower than the decomposition temperature of the substituted sodium aluminum hydride which is to be produced.

One suitable manner of carrying out the reaction is under reflux at substantially the boiling temperature of the reaction mixture. The liquid reaction medium preferred is benzene or toluene but, however, any of the liquid reaction media described above may be used.

The novel hydrides of the present invention are compounds of the general formula:

wherein x stands for an integral number between 1 and 2 inclusive, and wherein Q is an organic rest derived by splitting ofi an active hydrogen atom from one of the following compounds in which x has the same meaning as above:

(1) Tetarhydrofurfuryl alcohols, so as to form, for

instance,

Nan m oorrzl O 4-x (2) Tetrahydropyranyl alcohols, so as to form, for

instance,

(3) Ether alcohols formed for instance by alkylating one hydroxyl group in diols so as to form, for instance,

NaA1H [O(CH OR'] or two hydroxyl groups in triols, so as to form, for inwherein R is an organic rest selected from the group consisting of alkyl with 1-4 carbon atoms .and aryl with 6-8 carbon atoms, and z and w are each an integral number between 24 inclusive, and z and w may be the same or different.

(4) Polyether alcohols obtained by dehydration of ether alcohols and diols, so as to form.

wherein R has the same meaning as above and w and z are each integral numbers between 2 and 4 inclusive.

(5) Polyether alcohols obtained by dehydration of tetrahydrofurfuryl alcohols and diols, so as to form wherein z has the same meaning as above.

(6) Polyether alcohols obtained by the dehydration of tetrahydropyranyl alcohols and diols, so as to form wherein z has the same meaning as above.

(7) Any of the compounds described in numbered paragraphs 1-6 above, in which one or more or all oxygen atoms are replaced by sulphur atoms, so as to form wherein R is alkoxyalkyl of the formula RO(CH or R, and wherein R' has the same meaning as above. (8) An amino alcohol of the general formula wherein R" and R' each have the same meaning as R and R" and R may be identical or dilferent, so as phur as well as oxygen atoms.

Groups of compounds which fall within the scope of the present invention include:

, NaAlH; com-L NaAlHg O CHzo NaAlH, 0 (CH 0 CH wherein w is an integral number between 2 and 4 inclusive and x,.z, R, R" and R' havethe same meaning as described above.

6 More specifically, but not by way of limitation, the compounds of the present invention include:

NaAlHz OCHrL J NaAlHz 0 CH2 NS-AlHz 0 (CH2) 2N (CH3)2]2 NS-AlHz 0 (CH2) 2N (021119212 NaAlHz O (CH2)2N (CH2CH2O CH2) 212 NaAlH NaAlH OCHr- O NaAlH NaAlH NaAlH 0 (CH2) 2N (CH3) 2]: 0 H2) 2 2mm: 0 (CH2)2N (CH2CH2OCH3)2]:

CH2OCH3 NaAlH 0C C1120 CH3 3 NaAlH[O (CHmO (CH CH It is also within the scope of the present invention to provide a method of producing at least one sodium aluminum hydride selected from the group consisting of NaAlH and Na AlH comprising the step of reacting metallic sodium and metallic aluminum with hydrogen preferably at an elevated hydrogen gas pressure and at an elevated temperature in the presence of a substituted sodium aluminum hydride as defined hereinbefore.

According to a further variation, the present invention is also concerned with carrying out reducing and dehalogenizing reactions by reacting a reducible organic compound such as an aldehyde, ketone, ester, carboxylic acid, halide of carboxylic acid, dialkyl amides, diaryl amides and aromatic nitro compound, or with a halide which may be an organic or inorganic monoor polyhalide also including substituted halides such as silicon alkyl or aryl halides for instance of the general formula R SiX wherein R is alkyl or aryl and X is a halogen.

The substituted sodium aluminum hydrides of the pres ent invention may thus be used as reducing agents soluble in non-polar media and as catalysts for the direct synthesis of complex sodium aluminum hydrides from free elements, i.e., from sodium, aluminum and hydrogen.

These substituted complex sodium aluminum hydrides will reduce in non-polar media, e.g., in benzene, the derivatives of organic acids, ketones and aldehydes to alcohols in the same way and to the same extent as it would be possible with non-substituted complex aluminum hydrides in ethers. In contradistinction to the properties of the known complex aluminum hydrides, they will even dehalogenate the alkyl and aryl halides, and they will reduce the nitro derivatives to azo-compounds. All the aforementioned reactions will proceed in ethers as well as in non-polar media.

The following examples are given as illustrative without, however, limiting the invention to the specific details of the examples.

EXAMPLE I An apparatus as described in Example II was charged with 2.1 g. of an 80% solution of Na AlH (0.0164 mol) and 50 ml. of benzene. The mixture was refluxed under dropwise addition of 8.27 g. of Al(OCH CH OCHi [0.0328 mol] dissolved in ml. of benzene. The reaction mixture was kept boiling under stirring for an additional minutes. Upon subsequent filtration, and evaporation of the solvent, 9.36 of NaAlH (OCH CH OCH was obtained, i.e., 94.1% of the theory.

The starting compound Al[OCH CH OCH was prepared by the following reaction:

The above reaction was carried out with a 160% excess on CH OCH CH OH. (Instead of using an excess on CH OCH CH OH, the theoretically required amount may be used and the excess of this compound replaced with another solvent, preferably benzene or toluene.) The methyl alcohol evolved was distilled off from the reaction mixture during the reaction, using a rectification column. Subsequently to stripping off the methyl alcohol, the excess of CH OCH CH OH was stripped off under vacuum. The product of the reaction is a liquid highly viscous compound of the formula Al(OCH CI-I OCH intermiscible with benzene, toluene, and ethers in any ratio.

EXAMPLE II Into a three-necked round-bottom flask of 100 ml. volume, provided with a stirrer, a reflux water-condenser and dropping funnel, 1.7 g. of Na AlH of 85% purity was charged (the remaining 15% consisting of aluminum and silicon), and ml. of tetrahydrofurane was added. The mixture was heated to boiling and a solution of 8.26 g. Al[O.CH CH N(CH in 15 ml. tetrahydrofurane was added dropwise under stirring. The heating was discontinued after minutes and the mixture was cooled to 15 C. Subsequent to filtration, the tetrahydrofurane was stripped 01f from the filtrate, and the thus obtained residue was dried at 100 C. at a pressure of 0.1 mm. Hg; 9.1 g. of a compound of the formula NaAlH [O.CH CH N (CH 2 was obtained, i.e., 93.5% of the theory according to Equa- 7 tion 8. The (CH NCH CH OH required for preparation of Al[OCH CH N(CI-I was prepared by a reaction which is well known in the methylation of primary amines to convert the latter into tertiary amines, starting with H NCH CH OH, formaldehyde and formic acid. The starting Al[OCH CH N(CH was prepared from aluminum methylate in a manner similar to that described in Example I, with respect to the preparation of Al OCH CH OCH EXAMPLE III Into a 2.5 1. pressure vessel, 46 g. of sodium (2 moles), 32.9 g. of aluminum powder of 82% purity (the balance up to 100% consisting of aluminum oxide), 50.5 g. of NaAlH (OCI-I CH OCH (0.25 mole), and 500 ml. of benzene was added and a stirring bar inserted into the pressure vessel for stirring of the reaction mixture. Hydrogen was fed into the vessel to establish a pressure of 100 atoms. The reaction was then carried out at a temperature of 170 C. for a period of 3 hours. The reaction mixture was filtered and the solid residue extracted with benzene; 55.4 g. of solid Na AlH was obtained of 88.5% purity, i.e., 96.1% of the theory. The benzene filtrate contained dissolved sodium aluminum alkoxyhydrides which were being used as catalyst in the following synthesis.

8 EXAMPLE Iv NaAlHz [OCHt L O 2 or NaAlH [O(CH N(CH are used as a catalyst; the sulphur compounds, however, being less suitable than the other compounds of the formula NaAlH Q The pressure of hydrogen applied may be in a very broad range from 2 to 200 atmospheres. At pressures lower than 2 atmospheres, however, the reaction is too slow; increasing the pressure above 200 atmospheres does not influence the reaction rate substantially, thus a further increasing of the pressure above 200 atmospheres is not practical. The quantity of the catalyst applied can vary in the range from 0.5 to inrespect to the amount of sodium and aluminum used. In the specific Example III and Example IV, about 50% of the catalyst was used.

Smaller amounts of the catalyst, below 0.5% result in decreasing of the reaction rate.

Using a greater amount of catalysts is of no inconvenience as the catalyst may easily be recycled.

It is advisable to mill the reaction'mixture thoroughly prior to the actual synthesis.

EXAMPLE V Into a 1 liter three-necked vessel, provided with a stirrer, a water cooler, and dropping funnel were charged: 2.75 g. NaAlH [98.2%], 200 ml. benzene, and 8 g.

The reaction mixture was refluxed under dropwise addition of a solution of 21.9 g.

which corresponds to 98.16% of the theory.

The starting compound of the formula was prepared in toluene'by the well known reaction accounted for by the following equations was prepared from aluminum methylate by reactions similar to those'described in-Example I. The alcoholate The starting was prepared in a refluxing mixture of toluene, sodium hydride and @OCHZCIEOH in a 20% excess. The toluene and the excessive ether alcohol were stripped off in vacuo and the remaining portions of the said compounds Were distilled oif at 0.05 mm. Hg and 160 C.

EXAMPLE VI The same apparatus as in Example V was charged with 5.6 g. Na AlH [91.1%], 500 ml. benzene, and 26.1 g.

Na[ cmcnio ca -Q] The reaction mixture was refluxed under dropwise addition of a solution of 120 g.

in 200 ml. benzene across a period of 30 minutes. The reaction mixture upon treatment as described in Example V yielded 147.2 g.

i.e., 97.36% of the theory.

To prepare NaO 011201120 oa -Q and All: ocmcrno cal-Q] use was made of the same methods as described in Example V.

EXAMPLE VII The same apparatus as in Example V was charged with 2.75 g. NaAlH [9 8.2%], 2.5 g. NaH [96.0%] and 150 ml. toluene. The reaction mixture was refluxed under dropwise addition of a solution of 29.4 g.

EXAMPLE VIII Into the same apparatus as described in Example V, were charged: 2.75 g.. of NaAlH, [98.2%], 26.1 g. of

Na(oomomcmo) and 500 ml. of benzene. The reaction mixture was refluxed under simultaneous dropwise addition of a solution of 72 g.

in 150 ml. benzene, across a period of 45 minutes. Treatment of the reaction similar to that described in Example V gave 99.51 g.

i.e., 98.72% of the theory.

In the preparation of the starting compound use was made of .the same method as described in Example V.

EXAMPLE IX The same apparatus as in Example V was charged with 5.6 g. Na AlH [91.1%] and 250 ml. benzene. The reaction mixture was refluxed-under dropwise addition of a solution of 38.4 g. Al(O=CH;-C-H OCH CH OCH in ml. benzene. Further treating of the reaction mixture as described in Example V yielded 42 g.

NaAlH 2 which responds to 96.55% of the theory.

The alcoholates Al(OOH CH O'CH CH 'OCHQ was prepared from CH 'OCH CH OCH CH OH by the method described in Example I.

EXAMPLE X Into the same apparatus as used according to Example V, were charged: 2.75 g. NaAlH and ml. benzene. The reaction mixture was refluxed under dropwise addition of a solution of 41.5 g.

NaAl(OCHzCHrOCHrCHzCHrO-) in ml. benzene. The same treatment of the reaction mixture as in Example V gave 43.2 g.

which is 97.74% of the theory.

The

Q-oomomcmo cmcmon required for preparation of msoomcmoomcmomoQ) was prepared in the following manner; The sodium phe nolate was alkylated in boiling toluene with 6-0 CHzCHzCHzOH resulting from the reaction was isolated and converted by reaction with sodium hydride in boiling toluene into its alcoholate and the latter was alkylated with HOCH CH Cl giving a compound of the formula Q-oomomomo CH C H OH The starting complex alcoholate was prepared in the apparatus described in Example V in accordance with the following equation:

NaAlHi 4 Q-oomcmcmo 032011.011

NaAl [oomomocmomomoQ] 4H The alcohol was added dropwise to a 5% solution of sodium aluminum tetrahydride in tetrahydrofurane in the stoichiometrically required amount.

The reaction proceeded quantitatively under considerable evolution of heat and of hydrogen. After the evolution of hydrogen had stopped, tetrahydrofurane was distilled off and the product stripped ofi from the residues of tetrahydrofurane at 0.1 mm. Hg and 100"C.v

1 1 EXAMPLE XI The same apparatus as described in Example V was charged with 5.6 g. Na AlH (91.1%), 27.6 g.

and 600 ml. benzene. The reaction'mixture was refluxed under dropwise addition of a solution of 127.6 g.

in 250 ml. across 45 minutes. Upon treatment of the reactionmixt-ure as described in Example V, 154.0 g. of

was obtained, which corresponds to 96.13% of the theoretical yield.

The alcohol of the formula required for preparation of the starting al-coholate was prepared from 1,4-butanediol by converting one of the hydroxyl groups into alcoholate by reaction with sodium hydride in boiling toluene and subsequent alkylation with C H Br. The product obtained, i.e.,

was reconverted into the alcoholate form by reaction with sodium hydride in boiling toluene with C H O (CH Na subsequently alkylated with CICH CH 'OH, giving C H O(CH O(CH OH The starting alcoholate of the formula was prepared from aluminum methylate and C H 0(CH O(CH OH in the same manner as described in Example I. The compound of the formula NaO(CH O(OH- OC H was prepared by the reaction of sodium hydride with z s' 2) 4 2 )z in the same manner as described in Example V.

EXAMPLE XII The same apparatus as described in Example V was charged with 2.75 g. of NaAlH (98.2%), 2.5 g. NaH (96.0%), and 300 ml. toluene. The reaction mixture was refluxed under dropwise addition of a solution of Al[O(CHz)zOCH;-L O 2 in 100 ml. toluene. Upon treatment of the reaction mixture as described in Example V, 50 g. of

was obtained, i.e., 97.4% of the theory.

The

L iomowmhofi required for preparation of was prepared from and NaoCH CH OH in boiling toluene by the method described in Example V. The starting was prepared by the method described inExample I.

EXAMPLE XIII The same apparatus as described in Example V was charged with 5.6 g. Na AlI-I (91.1%) and 250 ml. tetrahydrofurane. The reaction mixture was refluxed under dropwise addition of a solution of 22.3 g.

EXAMPLE XIV The same apparatus as described in'Example V was charged with 5.6 g. Na AlH (91.1% 19.2 g.

and 450 ml. toluene. The reaction mixture was refluxed under dropwise addition of a solution of 85.5 g.

in 150 ml. toluene for a period of 40 minutes. Upon'treatment of the reaction mixture as described in Example V,

106 g. NaAlH[O(CH SC H was obtained, i.e.,

96.54% of the theoretical yield.

For preparation of the starting reactants, first a thioether alcohol was prepared from HOCH CH Br and C H SNa in boiling xylene. The C H SCH CH OH obtained was converted into its sodium alcoholate by the method of Example V and into its respective aluminate AI(OCH CH SC H by the method described in Example I. 1

EXAMPLE XV The same apparatus-as described in Example V was charged with 5.6 g. Na AlH (91.1%) and 350 ml. benzene. The reaction mixture was refluxed under dropwise addition of a solution of 59.5 g.

in 100 ml. benzene for a period of minutes. Upon treatment of the reaction mixture as described in Example NaAlHgl o (CH2)4S CH l O 2 which corresponds to 96.14% of the theory were obtained.

In preparation of the starting material first the compound of the formula o LCH SKIH MOH was prepared from L l-omsn by conversion of the latter into using sodium hydride in boiling toluene. The subsequent operation was alkylation of the mercaptide formed, i.e.,

of the mercaptide J-CHzSNa with HO(CH Br. The thereby obtained product LQlCHzMCH-MOH was converted into sodium alcoholate LQl-CHzS (CH2) AONa.

by the method of Example I.

EXAMPLE XVI The same apparatus as described in Example V was charged with 5.6 g. Na A1H (91.1%) and 250 ml. toluene. Under refluxing the reaction mixture, 34.2 g. A1[SC H OC H dissolved in 100 ml. tetrahydrofurane was added dropwise over a period of 45 minutes. Upon treatment of the reaction mixture as described in Example V, 38.6 g. NaAlH[SC H 0C I-I was obtained, i.e., 98.22% of the theory.

The required mercaptane C H OC H SH was prepared by conventional synthetic methods from via a thiouronian salt. The aluminium mercaptide was prepared from the mercaptane obtained, by the reaction with aluminum hydride in tetrahydrofurane in a solution containing stoichiometric ratios of the reactants.

The solution obtained was subsequently anlyzed and, upon adjustment of concentration, used directly in the above preparation of NaAlH [SC H OC H EXAMPLE XVII 14 the reaction with sodium hydride in boiling toluene and the mercaptide was subsequently treated under reflux with (CH O) SO added in a molar ratio of 1:1. The aluminum mercaptide was prepared in the same way as described in Example XVII.

EXAMPLE XVIII The same apparatus as described in Example V was charged with 5.6 g. Na A1H (91.1%) and 150 ml. tetrahydrofurane. Under refluxing of the reaction mixture, 50.7 g. A1[SC H N(C H dissolved in 250 ml. tetrahydrofurane was added dropwise over a period of 45 minutes. Upon treatment of the reaction mixture as described in Example V, 53.79 g. of

2[ 2 -1 2 5)2]2 was obtained, i.e., 96.41% of the theory.

The amino mercaptane required was prepared from (C H NCH CH Cl via the thiouronian salt. The

(C H NCH CH SH thus obtained was used in the preparation of from aluminum hydride and tetr-ahydrofurane in the same manner as described in Example XVI.

EXAMPLE XIX The same apparatus as described in Example V was charged with 5.6 g. Na A1H (91.1% and ml. tetrahydrofurane. The reaction mixture was refluxed under dropwise addition of a solution of 144.4 g.

in 500 ml. tetr-ahydrofurane. Upon treatment of the reaction mixture as described in Example V, g.

was obtained, i.e., 97.06% of the theory.

The necessary mercaptane was prepared from by substitution of the bromine atoms with SH groups via thiouronian salt. The SH(CH SH thus obtained was converted into its sodium salt by reaction with sodium hydride in boiling toluene; the salt was alkylated with ethyl bromide also in toluene. The C H S(CH SH thus obtained was used in the preparation of the complex mercaptide starting from sodium aluminum tetrahydride. The reaction was carried out in tetrahydrofurane under reflux with theoretical amounts of the reactants according to the following equation:

The thus prepared solution was used directly (subsequent to analysis and adjustment of the concentration) in the preparation of the respective organically substituted sodium aluminum hydride of this example.

EXAMPLE XX The same apparatus as described in Example V was charged with 5.6 g. Na AlH (91.1%) and 100 ml. tetrahydrofurane. The reaction mixture was refluxed under dropwise addition of a solution of 33.9 g.

in 20 m1. tetrahydrofurane for a period of 45 minutes. Upon treatment of the reaction mixture as described in Example V, 37.8 g. NaAlI-I [SC H N(CH was obtained, i.e., 96.9% of the theoretical yield. The required aminomercaptane was prepared from 15 via the thiouronian salt. By the procedure described in the Example XVIII, the compound (CI-I NC H SH was converted into the aluminum mercaptide A1[SC H N(CH )zla EXAMPLE XXI The same apparatus as described in Example V was charged with 55.2 g. NaAlI-I[OCH CH OCH and 200 ml. benzene. The reaction mixture was refluxed under addition of 15 g. ethyl benzoate with 50 ml. benzene for a period of 30 minutes. After an additional 2 hours of refluxing, the mixture was cooled, and hydrolysis and isolation yielded 8.76 g. benzyl alcohol, i.e., 81% of the theory.

EXAMPLE XXIII In a similar manner to Example XXII, the following compounds were reduced under substantially the same reaction conditions, and with the same solvents molar concentrations and molar ratios of the reactants:

Reaction time in yield; Starting compound Product hours percent (CH300)2O CzHsOH 2 91.2 1I-C3H7CO0C2H5 C4H9OH 2 89. CH COON (OHm C3H7OH 4 62.8

The procedure, however, is not limited to the use of the compounds given above. Under the same conditions any other compound of the type :NaAlH Q may be used as for example NaAlH (OCH CI-I OCH or NaAlH OCH OCH OCI-I To reduce 1 g. mol of a compound containing one single carbonyl group (CH O or CO) into the respective alcohol the theoretically necessary amount of NaAlI-IQ is equal to l/x gram mole of NaAlH Q' to reduce one gram mole of a compound containing one single carboxyl group in the molecule the amount necessary of the compound NaA1H Q4 is equal to 2/ x gram mole of NaAlH Q EXAMPLE XXIV In an apparatus as described in Example V, a suspension of 5.6 g. trisodium aluminum hexahydride of 91.1% purity in 250 ml. of benzene was prepared. The suspension was heated to boiling and a solution of 37.2 g.

in 80 ml. benzene was added dropwise over a period of 30 minutes. By the method of Example V, 39.8 g. of

was obtained, which corresponds to 94% of the theory.

The starting was prepared by reacting aluminummethylate with a solution of 00112011 in toluene as a solvent, in which solution toluene and were present in a ratio of .111; the said CH2OH O was used in an excess which corresponds to 150% of the theoretical amount needed. In accordance with Equation 1, methylalcohol was stripped off from the reaction mixture in a rectification column;-subsequently, toluene .was stripped off at atmospheric pressure and, finally, the excess of CH2OH O was stripped oif in a partial vacuum at a temperature of up to 150 C. The product was anon-distillable, highly viscous matter, intermiscible with benzene, toluene, and ethers in any ratio.

EXAMPLE XXV In the same apparatus as in Example V, a suspension of 5.6 g. trisodium aluminum hexahydride of 91.1% purity in 250 ml. benzene was prepared. The suspension was refluxed and a solution of 33.3 g.

Alrocn cn crr NwHsma in ml. benzene'added during a period of 30 minutes.

In the same manner as described in Example V, 36.7 'g.

of NaAlH ['OCH CH CH N(CH was obtained.

To prepare the starting reactant first 1 had to be prepared from HOCH CI-I CH NH by the conventional reaction with formaldehyde and formic acid; Al[OCH OH CH N(CH was then prepared from (CH NCH CH CH OH in the same manner as described in Example XXIV. The former compound is a highly viscous non-distillable liquid, intermiscible with benzene, toluene and ethers in any ratio.

EXAMPLE XXVI In the apparatus described in Example V, a suspension of 5 .6 g. trisodium aluminum hexahydride of 91.1% purity in 250 ml. of benzene was prepared. The suspension was refluxed and a solution of 55.5 g.

Al OCH CH N CH CH OCH 3 in 80 ml. benzene was added dropwise over a period of 30 minutes. In the same manner as described in Example V, 59.4 g. of NaAlH [OCH OH N(CH CH OCH 1 was obtained, i.e., 94.7% of the theory To prepare the starting reactant, first cmocn camncn cn on I had to be prepared according to the following equations:

18 EXAMPLE XXV III In the apparatus described in Example V, a suspension of 5.6 g. of trisodium aluminum hexahydride (0.05 mol) of 91.1% purity was prepared in 250 ml. benzene. The

suspension was refluxed and a solution of 38.4 g. of 3 2 2 2 2 Z 2 3 2 Al[OOI-I(OH OCH in 80 ml. benzene was added To a refluxing suspensing of sodium hydride in xylene overa period of 30 minutes. In the same manner as de- (200 ml. of xylene per 1 g m 11101 Sodium hy ri scribed in Example V, 55.6 g. of

Na (CH CH OH 3 NaA1H [OCH(CH -OC-H 2 Was added r pwi under Stirring, and heating was p was obtained, which corresponds to 95% of the theory. longed until evolution of hydrogen had substantially Th starting (CH OCH CHOH was prepared from PP Subsequently 3 )2 2 Was added under the glycerol by methylation of two hydroxyl groups by resame conditions, and the refluxing was resumed and cona ti ith odium hydride and (OH O) 80 in a similar tinned under the evolution of hydrogen terminated. The anner a de ribed in Example XXVI, The ether alcomixture Was allowed to cool and 1 00 ml. of a 60% Water hol btained was u ed in the reaction with aluminum solution of potassium hydroxide added per one gram mol ethoxide to prepare the starting Al[OCH(CH OOH of (CH O) SO used. Then, the reaction mixture was in th manner described in Example V. filtered, the solid phase washed with xylene and from the I Xylene solutions HOCH OH N(CH CH OCH was ex- EXAMPLE XXIX tracted with water, neutralized and slightly acidified with In the apparatus described 1n Example V, a suspension hydrochloric acid. The hydrochloride obtained was isowas prepared of 5.6 trisodium aluminum hexahydride of lated by evaporation of water in vacuo, and the base was a 91.1% purity in 200 ml. tetrahydrofurane. Under the set free by addition of a 70% water solution of potassium conditions described in Example V, a solution of 20.4 g. hydroxide which was added in a slight excess not higher of (n-C H O) Al in 200 ml. tetrahydrofurane was added. than 10% over the theoretically required amount. The Identical procedure as described in Example V afforded mixture was stirred with diethyl ether and the precipitated 24.1 g. of NaAlH l'ofi a' 'lnz, i.e., 94.3% of the potassium chloride was filtered off. The product theory.

EXAMPLES XXX T0 XL (CH3OCHZCH2)ZNCH2CH2OH In the apparatus described in Example V, and under was obtained from the ethereal solution by distillation and the same conditions as described therein, further comconverted into its aluminate in the same manner as depounds of the formula NaAlHQ were synthetized accordscribed in Example XXIV. ing to the equation EXAMPLE XXVI-I 1+ Q+ Qe+ Qe In the apparatus described in Example v, a suspension wherein the different radicals Q are defined in the Table 1 of 5.5 g. of 195 11111 of 91.1% purity was prepared in 250 belowml. benzene. The suspension was refluxed, and a solution In the apparatus descflbed pl V, a 51151161151911 f 72 3 A][OCH OH N(CH CH CH CH OcI-I i was prepared of 2.75 g. of sodium alumlnum tetrahydrlde 120 ml. benzene added dropwise over a period of 30 minof a P y of 11101 alcoholate utes. In the same way as described in Example V, 72.1 g. the typ Q Where"! Q agam has the Several meanings of NaAlH [OCH CH N(CH CH OH CH OCH was llsted m the table below. The reaction medium was 200 obtained which corresponds to 932% f the theory ml. benzene. The reaction mixture was refluxed at ambient The starting amino alcohol was prepared from Pmsstlre and a Solutlon of mol of Qa ill H O CH CH NH benzene was added dropwise across a period of 30 min- 2 2 2 utes. The reaction mixture was refluxed for an additional by alkylation f cH 0OH C-H CH CH CL Th latte 4 hours. Upon cooling to 15 C., the clear solution was compound was prepared by methylation of the hydroxyl filtered ofli and the solid residue containing mostly startgroup in 1,4-butane diol and by subsequent conversion of mateflals and impurities Was hed with benzene the second hydroxyl group into chloride by reaction with pp Ofi from the filtrate- From t e C ear Solution thionyl hl id Th necessary obtained benzene was distilled off and the collected product was dried in vacuo at 100 C. and 0.1 mm. Hg. [(OHaOCHzCHZCI-IZCHZ)2NCH2CH2O]3A1 The yields in gram and percent obtained with respect was prepared in the manner described in Examples '1 and to the ditferent specific reactants of Examples XXX to XXIV. XL are also indicated in Table 1.

TABLE 1 Starting compounds Product yield NaalHl NaQ in AlQ in NaAlH m g. g. g. in g. Percent 2. CH3O(CH2)zO- 14.7 37.8 52.1 96.5 2. 75 C1Hh0(CH2)30 16.8 14.1 59.9 94.1 2. 75 CH=O(CH7)9O- 16.8 44.1 60.4 95.0 2. 75 C1H50 (011910- 18.9 50.4 68.5 95.1

XXXIV 2.75 18.6 49.5 67.6 95.5

XXXV 2. 75 20. 7 55. 8 74. 4 94. 4

CHzO- 2. 75 (CHa)2N(CHz)z0- 16.7 43.7 60.5 96.1 2. 75 H N Hm0- 20.9 56.3 64.9 95.1 2.75 (GH3OCHzCHz)2N(CHz)2O 22.4 60.8 61.2 94.6 2. 75 (CH3OOH2)2CHO 21.3 57.6 79.3 96.1 2. 75 CH30(CH2)20(CH2)20 21.3 57.6 76.1 93.2

EXAMPLES XLI TO XLIII wherein the ditferent radicals Q are defined in the Table 2 below.

With the same result, any of the other compounds of the formulae NaAlH Q e.g.,

NaAlH [O(CH N(CH 12 NaAlHz [OCT- i312 may be used.

EXAMPLE XLVI The starting material used were throughout all the Ex- Into a pressure vessel of 1.5 1. volume a solution of amples 5.6 g. of Na AlH (0.05 mol) of 91.1% purity in 67 g. of NaAlH [O(CH OCH (0.33 mol.) in 500 250 m1. benzene and 0.1 mol AlQ in 100 ml. benzene. ml. of benzene was charged and a sealed glass ampulla The yields in grams and percent obtained with respect 15 containing 27.1 g. of SiHCl (0.2 mole) and 5 steel to the different specific reactants of Examples XLI to balls of a diameter of mm. were inserted into the XLIII are also indicated in Table 2. vessel. The pressure vessel was closed, flushed three TABLE 2 Starting compounds Product yield NaaAuIfi AlQa NELAIHZQQ Example in g. Q, in g. in g. Percent XLI 5.6 C2H5O(CH2)2O- 20.4 32.7 94.7 XLII 5.6 onnowrrmo- 33.6 36.9 95.3

XLIII 5.6 35.4. 93.0

EXAMPLE XLIV Into a pressure vessel of 2.5 1. volume were charged 23 g. of sodium (1 mole), 33 g. of aluminum powder (of 95% purity, containing 5% aluminum oxide), 400 ml. toluene and 9.2 g. of NaAlH [O(CH N(CH equal to 16% by Weight of the latter with respect to the amount of sodium and aluminum used. Hydrogen was introduced into the pressure vessel to establish a pressure of 150 atmospheres. The pressure vessel was heated to a temperature of 160 to 170 C. and the pressure therein Was kept at the level of 150 atmospheres. The reaction was finished after 4 hours and the pressure vessel cooled and emptied. The solid phase was extracted with tetrahydrofurane which was used in a quantity of 200 milliliters per each 10 grams of NaAlI-L; obtained. From the tetrahydrofurane extract 50.1 g. of NaAlH was obtained subsequent to evaporation, i.e., 92.6% of the theory.

As to the catalyst used and as to the amount of the latter applied conditions Were maintained as described in Example III. The optimum temperature range lies between 150 and 170 C. At temperatures below 150 C. the reaction is too slow or it does not proceed at all. At temperatures above 170 C. trisodium aluminum hexahydride is obtained as a by-product. It is also possible to work with stoichiometric amounts of sodium and aluminum; an excess on aluminum, however, is more advantageous (from 10 to 50%) so as to avoid excessive formation of trisodium aluminum hexahydride.

EXAMPLE XLV In the apparatus described in Example V, a solution of 13.4 g. of p-CH C H NO in 100 ml. benzene was added dropwise across a period of 30 minutes to a refluxing solution of 40.4 g. of NaA1H [O(CI-I OCH (0.2 mole) in 200 ml. benzene. The mixture was refluxed for one additional hour and, subsequently to cooling to 20 C., 200 ml. water was added and the mixture "was neutralized with theoretical amounts of sulfuric or hydrochloric acid. The solution was filtered, the benzene layer removed and 9.4 g. of the compound was obtained subsequently to evaporation of benzene. The yield was 92% of the theory.

EXAMPLE XLVII Under conditions identical with those described in Example XLVI, the reaction of 34 g. of silicon tetrachloride (0.2 mole) with g. of NaAlH [O(CH OCI-I (0.44 mole) in 500 ml. benzene was carried out. The reaction afforded 4.6 1. (20 C.) of silicon hydride, SiH i.e., 92% of the theory. Other compounds of the formula NaAlI-I,. Q.; may be used in a similar manner and with the same result.

EXAMPLE XLVIII Under conditions identical to those of Example XLVI, the reaction of 21 g. SiF, (0.2 mole) with 90 g.

NaAlHz 2OCH3] 2 (0.44 mole) in 500 ml. benzene was carried out, giving 4.85 l. of silicon hydride, SiH i.e., a yield of 97%. Other compounds of the formula NaAlH Q may be used in a similar manner and with the same result.

EXAMPLE XLIX Under conditions identical to those of Example XLVI, the reaction of 30 g. CH SiCl (0.2 mole) with (0.33 mole) in 500 ml. benzene was carried out. The reaction afforded 4.44 l. of CH SiH i.e., 89% of the theory. Other compounds of the formula NaAlI-I Q may be used in a similar manner and with the same result.

EXAMPLE L In the apparatus described in Example V, containing a solution of 33.3 g. of NaAlH [OCH CH OCH (0.165

EXAMPLES LI TO LIII Into a rotary pressure vessel of 1.5 1. working volume, a solution was introduced consisting of 500 ml. benzene having dissolved therein NaAlH [Cl-l CH N(CH in the amounts indicated in Table 3 below. 5 steel balls of a diameter of 30 mm. and a sealed glass ampulla containing the halide the formula of which and the amount in 300 ml. p-xylene was charged (the amount used of the former compound in the individual Examples LIV to LVI is given in Table 4). Subsequently, the mixture was refluxed under atmospheric pressure. To the refluxing solution was added dropwise across a period of min.- utes a solution of an aryl halide in 100 milliliters of p-xylene. The aryl halides used and the amounts thereof are also specified in Table 4 below. The reaction mixture was refluxed for an additional 2 hours. Upon cooling to 20 C., 100 ml. Water was added, and subsequently, 100 ml. of 20% hydrochlorine acid. The organic layer was quantitatively separated and neutralized by shaking with 5 ml. of a aqueous solution of potassium hydroxide, introduced into a 1 liter measuring flask, and xylene was added up to the required level.

The product was identified, the yield ascertained by means of gas chromatography.

TABLE 4 Starting compounds I NaAlHz OCH2-- Aryl halide O a Product yield In gram Example In g. In gram mol In g. mol Hydrocarbon in g. Percent LIV 30.5 0.12 0.2 Na hthalene 24.8... 96.8

LV- 30.5 0.12 1' 1 0.1 Benzene, 7.3.......... 93.5

I Br LVI 45.7 0.18 Br 0.1 Benzene, 7.2 92.2

Br- -Br 31.5

I Br

of which are given in Table 3 were also inserted into the EXAMPLE LVII pressure vessel. The pressure vessel was flushed with hydrogen and the ampulla was caused to break in, the A pressure vessel Of 2.51. working volume was charged manner described in Example XLVI. The pressure vessel was rotated under heating to a temperature of C. at which temperature the rotating vessel was kept for 2 hours. Upon cooling to 20 C., the gas evolved was discharged into a gas receptacle, the volume of the gas determined and the latter identified by means of gas chromatography.

with 69 g. metal sodium (3 mol.), 28.4 g. of aluminum powder of 90.1% purity (1 mol.), 114 g. of Na AlH of 89.8% purity (1 mol.), one liter of a xylene solution of 95 g. NaAlH [OCH CH N(CH and 1.4 l. of steel balls of S-mm. diameter. The pressure vessel was closed, flushed thoroughly with hydrogen, evacuated and heated to a temperature of to C. At this temperature,

TABLE 3 Starting compounds Alkyl halide Product; N8A1Hz=[OCHzCH:N(CHa)z]: In gram Hydrocarbon Example In g. In gram mols In g. mols liter/20 0. Percent LI 141 0.6 CHaCl, 50.5 1 CH 23.5 94 LII 282 1 CzHiBrz, 188 1 CRHO, 23.1 92 L111 141 0.5 CzHtJ', 166 1 CzHe, 23.8 95

EXAMPLES LIV TO LVI hydrogen was introduced into the vessel, and the partial Into the apparatus as described in Example V, a solu- 7 pressure of hydrogen was kept in a range of between 0.45

tion of N.....(....Lj)

to 0.55 atmosphere. When the reaction was finished and the consumption of hydrogen stopped, the presure vessel was cooled, emptied, the balls removed and the suspension obtained was treated in the manner described in 75 Example III. The synthesis afforded 205 g. of a slightly grayish matter containing 191 g. of trisodium aluminum hexahydride which corresponds to a yield of 9.4%.

The addition of trisodium aluminum hexahydride to the reaction mixture prior to the actual synthesis is only of importance for the milling of aluminum which otherwise would not proceed. Another material may be also used for this purpose, any inert material, as for instance aluminum oxide will give the desired result. The final product, however, is then contaminated with the inert material added.

As to the choice of the catalyst, the same will apply as stated in Example III.

Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can by applying current knowledge readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention and, therefore, such adapatations should and are intended to be comprehended within the meaning and range of equivalence of the following claims.

What is claimed as new and desired to be secured by Leters Patent is:

1. A substituted sodium aluminum hydride of the formula NaAlI-I wherein x is 1 or 2 and wherein Q is an organic residue derived by splitting off an active hydrogen atom from a compound selected from the ground consisting of:

(1) ether alcohols of the formula R'O(CH OH where R is alkyl of 1 to 4 carbon atoms and z is an integer from 2 to 4;

(2) polyether alcohols of the formula wherein n is an integer from 2 to 4 and R and 2 have the same meaning as in (1) above; (3) an amino alcohol of the general formula wherein R" and R' are each selected from the group consisting of RO(CH and R, and wherein R is selected from the group consisting of alkyl of 1 to 4 carbon atoms and aryl of 6 to 8 carbon atoms, and wherein 2 has same meaning as in (1) above.

2. The substituted Sodium aluminum hydride of claim 1, wherein Q is OR and R is alkoxy-alkyl or t-aminoalkyl, alkyl and alkoXy in these two radicals having from 2 to 4 atoms.

3. The sodium-aluminum hydride of claim 1, which has the formula NaAlH [O(CH OR]2, wherein R is alkyl having 1 to 4 carbon atoms and m is 2 or 3.

4. The sodium-aluminum hydride of claim 1, which is NaiA1{[O(CH OR}- wherein R is alkyl having 1 to 4 carbon atoms, m is 2 or 3 and w is an integer from 2 to 4.

5. The sodium-aluminum hydride of claim 1, which is wherein R" and R are alkyl having 1 to 4 carbon atoms and m is 2 or 3.

6. A composition as defined in claim 1, wherein said substituted sodium-aluminum hydride is selected from the group consisting of 7. A composition as defined in claim 1, wherein said substituted sodium aluminum hydride is selected from the group consisting of H!)2OCH3]2 2) 20 C21 5]: 2) 30 OHalz /CH;O CH NaAlHz O CH and 8. A substituted sodium aluminum hydride as defined in claim 7, and having the formula NaAlI-I [0 (CH OCH 2 9. A substituted sodium aluminum hydride as defined in claim 7, and having the formula /CH2O CH3 NaAlH 00s 011200113 3 NaAlH [O(CH2)2O(CH2)2OCHa]z References Cited UNITED STATES PATENTS 2,494,968 1/1950 Schlesinger et al 260-462 3,147,272 9/ 1964 Brown et a1 260-448 X 3,184,492 5/1065 Cole 260-448 3,060,216 10/ 1962 Hamprecht et a1 260-448 3,281,443 10/1966 Hunt 260-448 3,394,158 7/ 1968 Chini et a1 260-448 TOBIA-S E. LEVOW, Primary Examiner H. M. S. SNEED, Assistant Examiner U.S. Cl. X.R.

23-365; 252-431 R, 431 N; 260-327 R, 347.8, 345.9, 332.3 R 

1. A SUBSTITUTED SODIUM ALUMINUM HYDRIDE OF THE FORMULA NAA1HXQ-4, WHEREIN X IS 1 OR 2 AND WHEREIN Q IS AN ORGANIC RESIDUE DERIVED BY SPLITTING OFF AN ACTIVE HYDROGEN ATOM FROM A COMPOUND SELECTED FROM THE GROUND CONSISTING OF: (1) ETHER ALCOHOLS OF THE FORMULA R''O(CH2)ZOH WHERE R'' IS ALKYL OF 1 TO 4 CARBON ATOMS AND Z IS AN INTEGER FROM 2 TO 4; (2) POLYETHER ALCOHOLS OF THE FORMULA 